Abstract
It bas been shown that some tetra-coordinate phosphorus and arsenic radicals combine with oxygen to give peroxy radicals. The magnitude of the oxygen isotropic and anisotropic hyperfine coupling constants indicates that nearly all the unpaired spin is associated with the two oxygen nuclei with ca. 60% on the terminal oxygen. The large isotropic g-factors associated with Group VB peroxy radicals relative to alkylperoxy radicals is attributed to a small change in geometry of the peroxy function.The radicals with ap ∼ 9 G obtained during the reaction of photochemically generated tert-butoxy radicals with trialkylphosphites in the presence of oxygen are secondary species which appear to contain only one oxygen atom.
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